| Title | Synthetic and mechanistic aspects of a new method for ruthenium-metalation of porphyrins and Schiff-bases |
| Publication Type | Journal Article |
| Year of Publication | 2008 |
| Authors | Reboucas, JS, Cheu, ELS, Ware, CJ, James, BR, Skov, KA |
| Journal | Inorganic Chemistry |
| Volume | 47 |
| Pagination | 7894-7907 |
| Date Published | Sep |
| Type of Article | Review |
| ISBN Number | 0020-1669 |
| Keywords | 3-COMPONENT COUPLING REACTION, AQUEOUS-SOLUTION, CARBON-MONOXIDE, CATALYTIC-PROPERTIES, CRYSTAL-STRUCTURE, ELECTROCHEMICAL PROPERTIES, ORGANIC TRANSFORMATIONS, OXIDATION REACTION, REVERSIBLE BINDING, X-RAY-STRUCTURE |
| Abstract | A new method is presented for metalation of a wide range of free-base, neutral, cationic, and anionic porphyrins in refluxing dimethylformamide (DMF) using an easily prepared [Ru(DMF)(6)](OTf)(3) complex, and comparisons are made with the more familiar metalation procedure using Ru-3(CO)(12). Both procedures generate Ru-II(porp)(CO)L complexes (L = solvent); use of the Ru-III-triflate precursor gives yields comparable to, or greater than, those obtained with the carbonyl, and generates no Ru-chlorin impurities. Mechanistic studies on the meso-tetraphenylporphyrin system reveal that the DMF furnishes the CO, which in the presence of essential water reduces the metal, and metalation likely occurs via a Ru-II-CO species. Corresponding metalation of tetradentate Schiff-bases gives trans-[Ru-III(Schiff-base)(DMF)(2)]OTf complexes in yields of similar to 50%, a limitation being the accompanying hydrolysis of the Schiff-base through the presence of trace water. |
| URL | <Go to ISI>://000258709500057 |
